EP1711458B1 - Procede de production de sels de guanidinium - Google Patents

Procede de production de sels de guanidinium Download PDF

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EP1711458B1
EP1711458B1 EP05700969.8A EP05700969A EP1711458B1 EP 1711458 B1 EP1711458 B1 EP 1711458B1 EP 05700969 A EP05700969 A EP 05700969A EP 1711458 B1 EP1711458 B1 EP 1711458B1
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EP1711458A1 (fr
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Nikolai Ignatyev
Urs Welz-Biermann
German Bissky
Helge Willner
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/15—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/44—Nitrogen atoms not forming part of a nitro radical
    • C07D233/48—Nitrogen atoms not forming part of a nitro radical with acyclic hydrocarbon or substituted acyclic hydrocarbon radicals, attached to said nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds

Definitions

  • the invention relates to a two-stage process for the preparation of guanidinium salts with an anion selected from the group consisting of sulfonate, alkyl or aryl sulfate, hydrogen sulfate, imide, methanide, carboxylate, phosphate, phosphinate, phosphonate, borate, thiocyanate, perchlorate, fluorosilicate or nitrate and intermediates in this process.
  • an anion selected from the group consisting of sulfonate, alkyl or aryl sulfate, hydrogen sulfate, imide, methanide, carboxylate, phosphate, phosphinate, phosphonate, borate, thiocyanate, perchlorate, fluorosilicate or nitrate and intermediates in this process.
  • guanidinium salts are ideal compounds for use as ionic liquids, nonaqueous electrolytes, phase transfer catalysts or surfactants.
  • the field of ionic liquids is being intensively researched, since the application possibilities are manifold.
  • review articles on ionic liquids are R. Sheldon "Catalytic reactions in ionic liquids", Chem. Commun., 2001, 2399-2407 ; MJ Earle, KR Seddon “Ionic Liquids, Green Solvent for the Future", Pure Appl. Chem., 72 (2000), 1391-1398 ; P. Wasserscheid, W. Keim "Ionic Liquids - Novel Solutions for Transition-Metal Catalysis," Angew.
  • Guanidinium salts can be prepared by protonation of guanidines with strong acids or by alkylation of guanidines with alkylating reagents such as alkyl triflate according to the classical methods.
  • the guanidine moiety can be obtained by a variety of methods, for example, by reacting amines with thioureas, Chlorformamidiniumchloriden or aminoiminomethanesulfonic, the synthesis of complex substituted guanidines is often complicated and / or expensive ( DA Powell, J. Org. Chem., 68 (2000), 2300-2309 ; DHR Barton, J. Chem. Soc. Perkin Trans. I, (1982), 2085-2090 ).
  • Guanidinium chlorides can also be obtained directly by reaction of phosgeniminium chloride with a secondary amine ( T. Schlama et al, J. Org. Chem., 62 (1997), 4200-4202 ).
  • the conversion to guanidinium salts with anions such as hexafluorophosphate, tetrafluoroborate or bistrifluoromethanesulfonimidate corresponds to a salification, as shown NMM Mateus et al, Green Chemistry, 5 (2003), 347-352 known.
  • a disadvantage of this salification here is that the final products are contaminated with chloride ions, since the separation of the parallel ammonium chlorides is often very difficult.
  • the object of the present invention was therefore to provide a simple and inexpensive process for the preparation of guanidinium salts without the use of a guanidine as starting material which provides salts in high purity.
  • guanidinium salts of the formula (1) wherein the substituents R each independently represent the meaning of Hydrogen, straight-chain or branched alkyl having 1-20 C atoms, saturated, partially or completely unsaturated cycloalkyl having 3-7 C atoms which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more substituents R may be partially or completely substituted by halogen or partially substituted by CN or NO 2 and halogen is F, Cl, Br or I, wherein up to four substituents R may be connected in pairs by single or double bond and wherein one or two non-adjacent carbon atoms of one or more substituents R are substituted by atoms and / or atomic groups selected from the group -O-, -C (O) -, -C (O) O-, -S-, -S (O) -, -SO 2 -, -SO 3 -, -N ,
  • PL 170332 describes the compound 2-chloro-1,3-dimethylimidazolidinium perchlorate.
  • JP 2002260966 describes generically compounds with imidazolium, 3,4,5,6-tetrahydro-pyrimidinium and imidazolidinium cations in which the substituent R 2 can denote F between the nitrogen atoms of the heterocycles and anions selected from the group BF 4 - , PF 6 - , Cl - , CF 3 SO 3 - , AsF 6 - , N (SO 2 CF 3 ) 2 - , NO 3 - , ClO 4 - , Br - or I - , and the compounds 2-fluoro-1,3-dimethylimidazolium tetrafluoroborate, 2-fluoro-3,4,5,6-tetrahydro-1,3-dimethylpyrimidinium tetrafluoroborate and 2-fluoro-1,3-dimethylimidazolidinium tetrafluoroborate.
  • EP 0982 299 A1 describes tetraalkylfluoroformamidinium trifluoroacetate.
  • Suitable substituents R of the guanidinium cation are, in addition to hydrogen: C 1 - to C 20 -alkyl groups, in particular alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 C. -Atomen, and saturated or unsaturated, that is also aromatic, C 3 - to C 7 -cycloalkyl groups which may be substituted by C 1 - to C 6 -alkyl groups, in particular phenyl.
  • the six substituents R of the guanidinium cation may be identical or different, although not all six substituents may be hydrogen.
  • the C 1 -C 6 -alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1 , 2- or 2,2-dimethylpropyl, 1-ethylpropyl or hexyl.
  • Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1 , 4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl which may be substituted by C 1 to C 6 alkyl groups, again Cycloalkyl group or substituted with C 1 - to C 6 -alkyl cycloalkyl group may also be substituted by halogen atoms such as F, Cl, Br or I, in
  • the phenyl group can be replaced by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C (O) OC 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C (O) NR ' 2 , SO 2 OR ', SO 2 X', SO 2 NR ' 2 , SO 3 H or NHC (O) R' may be substituted, wherein X 'F, Cl or Br and R' has a meaning given above, for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-prop
  • a heterocycle is understood as meaning a saturated or unsaturated monocyclic or bicyclic heterocyclic radical having 5 to 13 ring members, where 1, 2 or 3 N and / or 1 or 2 S or O atoms may be present and the heterocyclic radical is mono- or polysubstituted by C 1 - to C 6 -alkyl, C 1 -C 6 alkenyl, NO 2, F, Cl, Br, I, OH, C 1 -C 6 alkoxy, CN, SCN, SCF 3, SO 2 CF 3 , C (O) OC 1 -C 6 alkyl, NH 2 , C 1 -C 6 alkylamino or C 1 -C 6 dialkylamino, COOH, C (O) NR ' 2 , SO 2 OR', SO 2 X ', SO 2 NR' 2 , SO 3 H or NHC (O) R 'may be substituted, wherein X' and R 'have the meaning given above.
  • the heterocyclic radical is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, more preferably 1,2,3-triazole-1, -4- or -5-yl, 1,2,4-triazole-1 , -4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4 or -5-yl 1,2,4-oxadiazol-3 or -5-yl, 1, 3,4-thiadiazol-2 or -5-yl, 1,2,4-thiadiazol-3 or -5-yl, 1,2,3-thiadiazol
  • substituents R can also be linked in pairs in such a way that mono-, bi- or polycyclic cations are formed.
  • examples of such guanidinium cations are: or where the substituents R may have a previously stated or particularly preferred meaning.
  • the carbocycles or heterocycles of the above-mentioned guanidinium cations can still be replaced by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 Alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C (O) OC 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C ( O) NR ' 2 , SO 2 OR', SO 2 NR ' 2 , SO 2 X', SO 3 H or NHC (O) R ', where X' and R 'are as defined above, substituted or unsub
  • Dihalogen compounds of the formula (2) wherein the substituents R have a meaning given in formula (1) or a preferred meaning and X is F, Cl or Br, with the proviso that not all four substituents R are simultaneously hydrogen, are usually commercially available or can be prepared by synthesis methods as known from the literature, for example in the standard works such Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart or off K. Ohno et al., Heterocycles, 59 (2003), 317-322 . AA Kolomeitsev et al., J. Fluorine Chem., 103 (2000), 159-162 or H. Wittmann et al, Eur. J. Inorganic. Chem., 8 (2001), 1937-1948 are known. One can also make use of known per se, not mentioned here variants.
  • Kt + A- (3) wherein A- has a meaning given in formula (1) and Kt + may be a proton, R " 3 Si, alkali or alkaline earth metal cation, ammonium cation, phosphonium cation or a cation of group 11 or 12, wherein R" are each independently phenyl or a linear or branched alkyl group having 1-6 C atoms, which may be substituted by phenyl, means are usually also commercially available or can be prepared by synthesis methods, as known from the literature, for example in the standard works such Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart . Encyclopedia of Reagents for Organic Synthesis, Ed.
  • EP 0929558 B1 or US 6,423,454 for fluoroalkyl phosphates EP 1174941 .
  • EP 1205480 or EP 1229038 are known for fluoroalkyl borates.
  • Kt + is, for example, NH 4 + , H + , Li + , Na + , K + , Rb + , Mg 2+ , Ca 2+ , Ba 2+ , Cu + , Cu 2+ , Ag + , Zn 2+ , Cd 2+ , Hg + or Hg 2+ , more preferably NH 4 + , H + , Li + , Na + , K + , Rb + or Ca 2+ , the charge being present in balanced form in the respective salt form of the formula (3).
  • a divalent cation two monovalent anions of the formula A - are required for charge balancing.
  • charge balancing of a divalent anion two monovalent ones are used Cations Kt + needed.
  • the proviso of the charge balance is of course also for compounds of formula (1) and formula (4).
  • the anion A- is selected from the group sulfonate, alkyl or aryl sulfate, hydrogen sulfate, imide, methanide, carboxylate, phosphate, phosphinate, phosphonate, borate, thiocyanate, perchlorate, fluorosilicate or nitrate.
  • Suitable organic groups R F or R 1 of the anion are: C 1 - to C 20 -, in particular C 1 - to C 12 -alkyl groups, C 2 - to C 20 -, in particular C 2 - to C 12 - Alkenyl groups or saturated or unsaturated, ie also aromatic, C 3 - to C 7 -cycloalkyl groups which may be substituted by C 1 - to C 6 -alkyl groups, in particular phenyl.
  • Suitable organic groups for R 1 are also C 2 - to C 20 -, in particular C 2 - to C 12 -alkynyl groups in question.
  • a straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present, is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, Hexenyl, heptenyl, octenyl, -C 9 H 17 , -C 10 H 19 to -C 20 H 39 ; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl.
  • a straight-chain or branched alkynyl having 2 to 20 C atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, Heptynyl, octynyl, -C 9 H 15 , -C 10 H 17 to -C 20 H 37 , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.
  • the groups R F are perfluorinated, ie all carbon atoms are not saturated with hydrogen, but with fluorine atoms.
  • the groups R 1 may be partially substituted with halogen atoms, in particular with F and / or Cl, CN or NO 2 .
  • R F or R 1 may also be connected in pairs in such a way by single or double bonds that mono- or bicyclic anions arise.
  • anions A - are given below: [CH 3 OSO 3 ] - , [C 2 H 5 OSO 3] - , [C (CN) 3 ] - , [CH 3 SO 3 ] - , [C 8 H 17 SO 3 ] - , [CH 3 C 6 H 4 SO 3 ] - , [CF 3 SO 3 ] - , [C 2 H 5 SO 3 ] - , [CF 3 CF 2 SO 3 ] - , [(CF 3 SO 2 ) 2 N] - , [(FSO 2 ) 2 N] - , [(CF 3 SO 2 ) (CF 3 CO) N] - , [(C 2 F 5 SO 2 ) (CF 3 CO) N] - , [(C 2 F 5 SO 2 ) 2 N] - , [(CF 3 SO 2 ) 3 C] - , [(C 2 F 5 SO 2 ) 3 C] - , [(C 2 F 5 SO 2 ) 3 C]
  • Preferred anions A - are [CH 3 OSO 3 ] - , [CH 3 SO 3 ] - , [CF 3 SO 3 ] - , [C 8 H 17 SO 3 ] - , [CH 3 C 6 H 4 SO 3 ] - , [C 2 F 5 SO 3 ] - , [PF 6 ] - , [(C 2 F 5 ) 3 PF 3 ] - , [(C 2 F 5 ) 2 PF 4 ] - , [(C 4 F 9 ) 3 PF 3] -, [(C 3 F 7) 3 PF 3] -, [(HO) 2 P (O) O] -, [(C 2 F 5) 2 P (O) O] -, [( CH 3 O) 2 P (O) O] - , [(C 2 F 5 ) P (O) O 2 ] 2- , [BF 4 ] - , [B (CN) 4 ] - , [B (CF 3 )
  • Preferred compounds of the formula (3) are Na [OSO 2 OCH 3 ], Na [SO 3 CH 3 ], HSO 3 CH 3 , Na [SO 3 CF 3 ], HSO 3 CF 3 , Ca [SO 3 CF 3 ] 2 , (CH 3 ) 3 Si [ SO 3 CF 3 ], CH 3 C 6 H 4 SO 3 H, Na [C 2 H 5 SO 3 ], C 2 H 5 SO 3 H, Na [CF 3 CF 2 SO 3 ], C 2 F 5 SO 3 H, Li [(CF 3 SO 2 ) 2 N], H [(CF 3 SO 2 ) 2 N], Li [(C 2 F 5 SO 2 ) 2 N], Li [(CF 3 SO 2 ) 3 C ], H [(CF 3 SO 2 ) 3 C], Li [(C 2 F 5 SO 2 ) 3 C], K [(FSO 2 ) 3 C], Na [CH 3 C (O) O], CF 3 COOH, Na [C 2 H 5 C (O) O], H [CF 3 CF 2 C (O) O], H
  • Particularly preferred compounds of the formula (3) are H [P (C 2 F 5 ) 3 F 3 ] * 5 H 2 O, Li [(CF 3 SO 2 ) 2 N], H [SO 3 CF 3 ], Ca (SO 3 CF 3 ) 2 ], Na [OSO 2 OCH 3 ], (CH 3 ) 3 Si [SO 3 CF 3 ], Na [ClO 4 ], H [SO 3 C 6 H 4 CH 3 ], H [ (CF 3 SO 2 ) 2 N], H 3 PO 4 , Na [(CH 3 O) 2 P (O) O], H [O (O) P (C 2 F 5 ) 2 ], Rb [N ( CF 3 ) 2 ], Na [SO 4 CH 3 ] or H 2 SO 4 .
  • the reaction of the dihalogeno compounds of the formula (2) with compounds of the formula (3) can advantageously be carried out in water, temperatures of 0 ° -150 ° C., preferably 0 ° -40 ° C., being suitable. Most preferably, the reaction is carried out at room temperature.
  • the reaction may take place in organic solvents at temperatures between -50 ° and 150 ° C.
  • Suitable solvents are here water-miscible solvents such as dimethoxyethane, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, propionitrile, methanol, ethanol or isopropanol or mixtures with each other or with water.
  • Acetonitrile is a preferred organic solvent.
  • the reaction is preferably carried out at 0 ° -100 °, particularly preferably at 10 ° -70 ° C., most preferably at room temperature.
  • reaction of the dihalogen compounds of the formula (2) with compounds of the formula (3) can also be carried out without the use of solvents, namely at temperatures at which the dihalogen compound of the formula (2) is liquid.
  • reaction under a protective gas atmosphere is possible and preferable for oxidation-sensitive starting materials.
  • the compounds of the formula (2) are reacted with compounds of the formula (3) in equimolar amounts or with an excess of the compound of the formula (3). Preference is given to using an excess of from 5 to 20% of compound of the formula (3).
  • the compounds of formula (3) having as counterion [N (CF 3 ) 2 ] - with dichloro or dibromo compounds of the formula (2), it is advantageous, the compound of formula (3) in at least two molar Amount to use.
  • the compounds of formula (4) resulting from this first reaction where the substituents R, X and A - have one of the meanings given above or preferably given meanings, can be isolated with very good yield, generally more than 80%, preferably more than 90%.
  • the advantage here is that the separation of the resulting inorganic salts KtX is unproblematic and the compounds of formula (4) are not contaminated by halogen anions X - .
  • the substituents R in formula (5) are each, independently of one another, preferably hydrogen, straight-chain or branched alkyl having 1-20 C atoms or saturated, partially or completely unsaturated cycloalkyl having 3-7 C atoms, which is substituted by alkyl groups having 1-6 C Atoms can be substituted.
  • Preferred compounds of the formula (5) are ammonia, methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine, cyclohexylamine, dicyclohexylamine or lithium dimethylamide.
  • Particularly preferred compounds of the formula (5) are ethylamine, dimethylamine, diethylamine, dibutylamine, dicyclohexylamine, or lithium dimethylamide.
  • the second reaction of the chloroformamidinium salts of the formula (4) with compounds of the formula (5) may be carried out at a temperature be in which at least one of the two starting materials is liquid.
  • the use of solvents can then advantageously be dispensed with.
  • the reaction takes place at temperatures of 15 ° -100 ° C, more preferably at 50 ° -70 ° C or room temperature.
  • the reaction may take place in organic solvents at temperatures between -50 ° and 150 ° C.
  • Suitable solvents are here water-miscible solvents such as dimethoxyethane, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, propionitrile, methanol, ethanol or isopropanol or mixtures with each other or with water.
  • a water-immiscible organic solvent for example, dichloromethane or chloroform, preferably chloroform.
  • the reaction is preferably carried out at 10 ° -70 ° C., more preferably at 40 ° -50 ° C. or room temperature.
  • the reaction can also be advantageously carried out in water, with temperatures of 0 ° -150 ° C are suitable. Reactions in water preferably take place at room temperature.
  • reaction under a protective gas atmosphere is possible and preferable for oxidation-sensitive starting materials. It is likewise carried out under atmospheric pressure, the reaction advantageously taking place, for example, with ammonia, methylamine or dimethylamine, ie gaseous or readily volatile compounds of the formula (5), in closed vessels.
  • Step 2 of the process according to the invention can also be carried out under pressure, with a pressure of up to 50 bar being advantageous.
  • the compounds of the formula (4) are reacted with compounds of the formula (5) in an equimolar amount.
  • An excess of compounds of formula (5) may be advantageous.
  • guanidinium salts of the formula (1) resulting from this second step, as described above, can be isolated in very good yield, generally more than 80%, preferably more than 90%.
  • Guanidinium salts of the general formula (1) are preferably used in the process according to the invention.
  • the substituents R are each independently of one another hydrogen or a straight-chain or branched alkyl group having 1-12 C atoms, in particular 1, 2, 3, 4, 5, 6, 7 or 8 C atoms, with the proviso that not all six substituents R are hydrogen, or at least two substituents R are connected to each other by single or double bonds, so that a monocyclic cation is formed and the counter anion A - has one of formula (3) or a preferred or very preferred meaning.
  • Guanidinium salts of the formula (1) are very particularly preferably prepared by the process according to the invention, where the substituents R are each independently of one another methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n -Hexyl, n-octyl, cyclohexyl or phenyl or two substituents R are connected together so that an imidazolidinium cation is formed and the counter anion A - has one of formula (3) or a preferred or very preferred meaning.
  • the intermediate compounds of the formula (4) obtained according to the first stage of the process according to the invention are also suitable compounds for use as ionic liquids because of their properties.
  • substituents R are hydrogen or a straight-chain or branched alkyl group having 1-12 C atoms, in particular 1, 2, 3, 4, 5, 6, 7 or 8 C atoms, with the proviso that not all four substituents R are hydrogen, or at least two substituents R are connected to each other by single or double bonds, so that a monocyclic cation is formed and the counteranion A - [CH 3 OSO 3 ] - , [C 2 H 5 OSO 3 ] - , [C (CN) 3 ] - , [CH 3 SO 3 ] - , [C 8 H 17 SO 3 ] - , [CH 3 C 6 H 4 SO 3 ] - , [C 2 H 5 SO 3 ] - , [CF 3 CF 2 SO 3 ] - , [(FSO 2 ) 2 N] - , [(CF 3 SO 2 ) (CF 3 CO) N] - , [(C 2 FSO 2 ) 2 N] - , [(
  • the NMR spectra were measured on solutions in deuterated solvents at 20 ° C on a Bruker Avance 250 spectrometer.
  • the measurement frequencies of the various cores are: 1 H: 250.13 MHz, 19 F: 235.357 MHz and 31 P: 101.254 MHz.
  • the referencing method is specified separately for each spectrum or for each data record.
  • 1,3-Dimethyl-2-chloroimidazolidinium is obtained Tris (pentafluoroethyl) trifluorophosphate in a yield of 95.9% based on dichloroimidazolidine. Mp: 151-152 ° C 1 H NMR (reference: TMS internal, CD 3 CN), ppm: 3.10s (2CH 3 ), 3.90s (2CH 2 ).

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Claims (17)

  1. Procédé pour la préparation de sels de guanidinium de la formule (1)
    Figure imgb0080
     dans laquelle les substituants R, dans chaque cas indépendamment les uns des autres, présentent la signification de :
    hydrogène,
    alkyle en chaîne droite ou ramifié comportant 1-20 atomes de C,
    cycloalkyle saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes alkyle comportant 1-6 atomes de C,
    où un ou plusieurs substituants R peuvent être partiellement ou totalement substitués par halogène ou partiellement substitués par CN ou
    NO2 et halogène représente F, Cl, Br ou I,
    où jusqu'à quatre substituants R peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et où un atome de carbone ou deux atomes de carbone non adjacents d'un ou de plusieurs substituants R peut/peuvent être remplacé(s) par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O- et -P(R')2=N-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué
    et
    A- est un sulfonate, alkyl- ou arylsulfate, hydrogènesulfate, imide, méthanide, carboxylate, phosphate, phosphinate, phosphonate, borate, thiocyanate, perchlorate, fluorosilicate ou nitrate,
    par réaction d'un composé de la formule (2)
    Figure imgb0081
    où les substituants R présentent une signification indiquée dans le cas de la formule (1) et X représente F, Cl ou Br,
    avec un composé de la formule (3)

            Kt+ A-     (3),

    dans laquelle A- présente une signification indiquée dans le cas de la formule (1) et
    Kt+ peut être un proton, R"3Si, un cation de métal alcalin ou alcalino-terreux, un cation d'ammonium, un cation de phosphonium ou un cation pris parmi le groupe 11 ou 12,
    où R", dans chaque cas indépendamment des autres, représente phényle ou un groupe alkyle linéaire ou ramifié comportant 1-6 atomes de C, lequel peut être substitué par phényle,
    et par réaction qui suit du composant résultant de la formule (4)
    Figure imgb0082
    où les substituants R, X et A- présentent une signification indiquée dans le cas de la formule (1) ou (2),
    avec des composés de la formule (5)
    Figure imgb0083
    où les substituants R présentent une signification indiquée dans le cas de la formule (1) et
    M représente hydrogène, un métal alcalin ou un métal alcalino-terreux.
  2. Procédé selon la revendication 1, caractérisé en ce que des composés de la formule Kt+ A- (3) sont utilisés, où Kt+ présente une signification indiquée dans le cas de la revendication 1 et
    A- est choisi parmi le groupe
    [R1OSO3]-, [R1SO3]-, [RFSO3]-, [(FSO2)2N]-, [(RFSO2)2N]-, [(RFSO2)(RFCO)N]-, [(RFSO2)3C]-, [(FSO2)3C]-, [R1CH2C(O)O]-, [RFC(O)O]-, [P(CnF2n+1-mHm)yF6-y]-, [P(C6F5)yF6-y]-, [(R1O)2P(O)O]-, [R1 2P(O)O]-, [R1P(O)O2]2-, [RF 2P(O)O]-, [RFP(O)O2]2-, [BF4-zRF z]-, [BF4-z(CN)z]-, [B(C6F5)4]-, [B(OR1)4]-, [N(CN)2]-, [C(CN)3]-, [N(CF3)2]-. [HSO4]-, [SiF6]2-, [ClO4]-, [SCN]- et [N03] -,
    où les substituants RF, dans chaque cas indépendamment des autres, présentent la signification de
    alkyle perfluoré et en chaîne droite ou ramifié comportant 1-20 atomes de C,
    alkényle perfluoré et en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons doubles,
    cycloalkyle perfluoré et saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes perfluoroalkyle,
    où les substituants RF peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et
    où un atome de carbone ou deux atomes de carbone non adjacents du substituant RF qui ne sont pas à la position α sur l'hétéroatome peut/peuvent être remplacé(s) par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -S-, -S(O)-, -SO2-, -N=, -N=N-, -NR'-, -PR'- et -P(O)R'-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué,
    où les substituants R1, dans chaque cas indépendamment des autres, présentent la signification de
    alkyle en chaîne droite ou ramifié comportant 1-20 atomes de C, alkényle en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons doubles,
    alkynyle en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons triples,
    cycloalkyle saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes alkyle comportant 1-6 atomes de C,
    où les substituants R1 peuvent être partiellement substitués par CN, NO2 ou halogène et
    halogène représente F, Cl, Br ou I,
    où les substituants R1 peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et
    où un atome de carbone ou deux atomes de carbone non adjacents des substituants R1 qui ne sont pas à la position α sur l'hétéroatome peut/peuvent être remplacé(s) par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, P(O)R'O-, OP(O)R'O-, -PR'2=N-, -C(O)NH-, -C(O)NR'-, -SO2NH- ou -SO2NR'-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué
    et les variables
    n représente 1 à 20,
    m représente 0, 1, 2 ou 3,
    y représente 0, 1, 2, 3 ou 4 et
    z représente 0, 1, 2, 3 ou 4.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que A- est choisi parmi le groupe
    [CH3OSO3]-, [C2H5OSO3]-, [C(CN)3]-,
    [CH3SO3]-, [C8H17SO3]-, [CH3C6H4SO3]-, [CF3SO3]-, [C2H5SO3]-, [CF3CF2SO3]-, [(CF3SO2)2N]-, [(FSO2)2N]-, [(CF3SO2)(CF3CO)N]-, [(C2F5SO2)(CF3CO)N]-, [(C2F5SO2)2N]-, ((CF3SO2)3C]-, [(C2F5SO2)3C]-, [(FSO2)3C]-, [CH3C(O)O]-, [C2H5C(O)O]-, [CF3C(O)O]-, [CF3CF2C(O)O]-, [PF6]-, [P(C2F5)3F3]-, [P(C4F9)3F3]-, [P(CF3)3F3]-, [P(C2F4H)(CF3)2F3]-, [P(C2F3H2)3F3]-, [P(C2F5)(CF3)2F3]-, [P(C6F5)3F3]-, [P(C3F7)3F3]-, [P(C2F5)2F4]-, [(HO)2P(O)O]-, [(CH3O)2P(O)O]-, [(C2H5O)2P(O)O]-, [(C2F5)2P(O)O]-, [(C2F5P(O)O2]2-, [P(C6F5)2F4]-, [(CH3)2P(O)O]-, [CH3P(O)O2]2-, [(CF3)2P(O)O]-, [CF3P(O)O2]2-, [BF4]-, [BF3(CF3)]-, [BF2(C2F5)2]-, [BF3(C2F5)]-, [BF2(CF3)2]-, [B(C2F5)4]-, [BF3(CN)]-, [BF2(CN)2]-, [B(CN)4]-, [B(OCH3)4]-, [B(CF3)4]-, [B(OCH3)2(OC2H5)2]-, [B(O2C2H4)2]-, [B(O2C2H2)2]-, [B(O2C6H4)2]-, [N(CN)2] -, [N(CF3)2]-, [HSO4]-, [ClO4]-, [SiF6]-, [SCN]- ou [NO3]-.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le substituant X dans des composés dihalogène de la formule (2) selon la revendication 1 représente fluor ou chlore.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que le substituant R dans des composés de la formule (5) selon la revendication 1, dans chaque cas indépendamment des autres, présente la signification de
    hydrogène,
    alkyle en chaîne droite ou ramifié comportant 1-20 atomes de C ou
    cyloalkyle saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes alkyle comportant 1-6 atomes de C.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que la première étape du procédé est mise en oeuvre dans l'eau.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que la première étape du procédé est mise en oeuvre à des températures de 0° à 150°C.
  8. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que la première étape du procédé est mise en oeuvre dans un solvant organique.
  9. Procédé selon une ou plusieurs des revendications 1 à 5 et 8, caractérisé en ce que la première étape du procédé est mise en oeuvre à des températures de -50° à 150°C.
  10. Procédé selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que la seconde étape du procédé est mise en oeuvre sans solvant.
  11. Procédé selon une ou plusieurs des revendications 1 à 10, caractérisé en ce que la seconde étape du procédé est mise en oeuvre à une température à laquelle au moins un composant est liquide.
  12. Procédé selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que la seconde étape du procédé est mise en oeuvre dans un solvant organique.
  13. Procédé selon une ou plusieurs des revendications 1 à 9 et 12, caractérisé en ce que la seconde étape du procédé est mise en oeuvre à des températures de -50° à 150°C.
  14. Procédé selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que la seconde étape du procédé est mise en oeuvre dans l'eau.
  15. Procédé selon une ou plusieurs des revendications 1 à 9 et 14, caractérisé en ce que la seconde étape du procédé est mise en oeuvre à des températures de 0° à 150°C.
  16. Composés de la formule (4)
    Figure imgb0084
     dans laquelle les substituants R, dans chaque cas indépendamment les uns des autres, présentent la signification de
    hydrogène,
    alkyle en chaîne droite ou ramifié comportant 1-20 atomes de C, cycloalkyle saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes alkyle comportant 1-6 atomes de C,
    où un ou plusieurs substituants R peuvent être partiellement ou totalement substitués par halogène ou partiellement substitués par CN ou NO2 et
    halogène représente F, CI, Br ou I,
    où jusqu'à quatre substituants R peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et où un atome de carbone ou deux atomes de carbone non adjacents d'un ou de plusieurs substituants R peut/peuvent être remplacé(s) par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O-, et -P(R')2=N-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué,
    X représente F, Cl ou Br,
    étant entendu que les quatre substituants R ne sont pas tous simultanément hydrogène et
    A- est choisi parmi le groupe
    [R1OSO3]-, [R1SO3]- , [RFSO3]-, [(FSO2)2N]-, [(RFSO2)(RFCO)N]-, [(RFSO2)3C]-, [(FSO2)3C]-, [R1CH2C(O)O]-, [P(CnF2n+1-mHm)yF6-y]-, [P(C6F5)yF6-y]-, [(R1O)2P(O)O]-, [R1 2P(O)O]-, [R1P(O)O2]2-, [RF 2P(O)O]-, [RFP(O)O2]2-, [BF4-zRF z]-, [BF4-z(CN)z]-, [B(C6F5)4]-, [B(OR1)4]-, [N(CN)2]-, [(CN3)C]-, [N(CF3)2]-, [SiF6]2- et [SCN]-,
    où [CF3SO3]- est exclu et
    où les substituants RF, dans chaque cas indépendamment des autres, présentent la signification de
    alkyle perfluoré et en chaîne droite ou ramifié comportant 1-20 atomes de C,
    alkényle perfluoré et en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons doubles,
    cycloalkyle perfluoré et saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes perfluoroalkyle,
    où les substituants RF peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et
    où un atome de carbone ou deux atomes de carbone non adjacents du substituant RF qui ne sont pas à la position α sur l'hétéroatome peut/peuvent être remplacé(s) par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -S-, -S(O)-, -SO2-, -N=, -N=N-, -NR'-, -PR'- et -P(O)R'-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué,
    où les substituants R1, dans chaque cas indépendamment des autres, présentent la signification de
    alkyle en chaîne droite ou ramifié comportant 1-20 atomes de C, alkényle en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons doubles,
    alkynyle en chaîne droite ou ramifié comportant 2-20 atomes de C et une ou plusieurs liaisons triples,
    cycloalkyle saturé, partiellement ou totalement non saturé comportant 3-7 atomes de C, lequel peut être substitué par des groupes alkyle comportant 1-6 atomes de C,
    où les substituants R1 peuvent être partiellement substitués par CN, NO2 ou halogène et
    halogène représente F, CI, Br ou I,
    où les substituants R1 peuvent être connectés les uns aux autres par paires au moyen d'une liaison simple ou double et
    où un atome de carbone ou deux atomes de carbone non adjacents du substituant R1 qui ne sont pas à la position α sur l'hétéroatome peut/ peuvent être remplacé() par des atomes et/ou des groupes d'atomes choisis parmi le groupe -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, P(O)R'O-, OP(O)R'O-, -PR'2=N-, -C(O)NH-, -C(O)NR'-, -SO2NH- ou -SO2NR'-, où R' représente alkyle non fluoré, partiellement fluoré ou perfluoré comportant 1-6 atomes de C, cycloalkyle saturé ou partiellement non saturé comportant 3-7 atomes de C, phényle non substitué ou substitué ou un hétérocycle non substitué ou substitué
    et les variables
    n représente 1 à 20,
    m représente 0, 1, 2 ou 3,
    y représente 1, 2, 3 ou 4 et
    z représente 1, 2, 3 ou 4.
  17. Composés selon la revendication 16, caractérisés en ce que les substituants R représentent hydrogène ou un groupe alkyle en chaîne droite ou ramifié comportant 1-12 atomes de C,
    étant entendu que les quatre substituants R ne sont pas tous hydrogène ou qu'au moins deux substituants R sont connectés l'un à l'autre par des liaisons simples ou doubles pour former un cation monocyclique et
    le contre-anion A- représente
    [CH3OSO3]-, [C2H5OSO3]-, [C(CN)3]-,
    [CH3SO3]-, [C8H17SO3]-, [CH3C6H4SO3]-, [C2H5SO3]-, [CF3CF2SO3]-,
    [(FSO2)2N]-, [(CF3SO2)(CF3CO)N]-, [(C2F5SO2)(CF3CO)N]-,
    [(CF3SO2)3C]-, [(C2F5SO2)3C]-, [(FSO2)3C]-, [CH3C(O)O]-,
    [C2H5C(O)O]-, [P(C2F5)3F3]-, [P(C4F9)3F3]-, [P(CF3)3F3]-,
    [P(C2F4H)(CF3)2F3]-, [P(C2F3H2)3F3]-, [P(C2F5)(CF3)2F3]-, [P(C6F5)3F3]-,
    [P(C3F7)3F3]-, [P(C2F5)2F4]-, [(HO)2P(O)O]-, [(CH3O)2P(O)O]-,
    [(C2H5O)2P(O)O]-, [(C2F5)2P(O)O]-, [(C2F5)P(O)O2]2-, [P(C6F5)2F4]-,
    [(CH3)2P(O)O]-, [CH3P(O)O2]2-, [(CF3)2P(O)O]-, [CF3P(O)O2]2-,
    [BF3(CF3)]-, [BF2(C2F5)2]-, [BF3(C2F5)] -, [BF2(CF3)2 -, [B(C2F5)4]-,
    [BF3(CN)]-, [BF2(CN)2]-, [B(CN)4]-, [B(OCH3)4]-, [B(CF3)4]-,
    [B(OCH3)2(OC2H5)2]-, [B(O2C2H4)2]-, [B(O2C2H2)2]-, [B(O2C6H4)2]-,
    [N(CN)2] -, [N(CF3)2]-, [SiF6]- ou [SCN]-.
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US7439395B2 (en) 2008-10-21
US20070135645A1 (en) 2007-06-14
EP1711458A1 (fr) 2006-10-18
ES2426171T3 (es) 2013-10-21
JP2007519760A (ja) 2007-07-19
DE102004005404A1 (de) 2005-08-25
WO2005075413A1 (fr) 2005-08-18

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